Work piece with a hard film of alcr-containing material, and process for its production

ABSTRACT

A work piece or structural component is coated with a system of film layers at least one of which is composed of (Al y Cr 1-y )X, where X=N, C, B, CN, BN, CBN, NO, CO, BO, CNO, BNO or CBNO and 0.2≦y&lt;0.7, with the composition within said film being either essentially constant or varying over the thickness of the film continually or in steps, as well as a process for producing it.

This invention relates to the technology involving work pieces that arecoated with a system of thin films including at least one layer of an(Al_(y)Cr_(1-y))X composition as specified in claims 1 and 2. Theinvention further relates to a PVD process for depositing at least one(Al_(y)Cr_(1-y))X-film on a work piece as specified in claim 16.

Specifically, this invention encompasses the following:

-   -   Hard-material-coated work pieces with one or with a sequence of        several different films of aluminum chrome nitride and/or        carbonitride.    -   Tools coated with aluminum chrome nitride or carbonitride films,        in particular cutting and machining tools (drills, routers,        indexable inserts, screw taps, shapers, hobs, dies, swages,        drawing punches etc.), and the use of such tools.    -   Components coated with AlCrN or AlCRCN films, in particular        components in the realm of mechanical engineering/machine        building, such as gears, pumps, cup rams, piston rings, injector        needles, complete bearing assemblies or their individual        components, and the use of such components.    -   A process for producing films of aluminum chrome nitride and/or        carbonitride with a defined layer structure.

Various types of AlCrN films have been known in prior art. For example,JP 09-041127 describes a wear-resistant hard thin film of the followingcomposition: (Al_(1-y)X_(y)) Z, where X=Cr, V or Mg, Z=N, C, B, CN, BNor CBN and 0<y≦0.3. That film has been successfully used for extendingthe life of indexable inserts.

In “Multicomponent hard thin films . . . ”, Thin Films (Proc. 4^(th)Int. Sympos. Trends & New Applications of Thin Films, 1993), DGMInfo.gesellschaft Oberursel, 1993, p. 73, D. Schulz and R. Wilbergdescribe a CrAlN film which according to a drill test doubles the lifeof a drill bit coated with TiAlN. The film was deposited by a hollowcathode process which, however, entails strong fluctuations in thechrome/aluminum distribution in the (CrAl)N layer due to a discontinuousevaporation pattern.

In “Oxidation resistance of Cr_(1-x)Al_(x)N & Ti_(1-x)Al_(x)N films”,Surf. & Coat. Tech., Vol. 165, 2 (2003), p. 163-167, M. Kawate mentionsa Cr_(1-x)Al_(x)N film which, with a high Al content and a wurtzitestructure, displays improved oxidation resistance in comparison withconventional TiAlN films.

In “Investigations of Mechanical & Tribol. Properties of CrAlN-C ThinCoatings Deposited on Cutting Tools”, E. Lugscheider, K. Bobzin, K.Lackner compare arc-deposited CrAlN films with CrAlN coatings that havebeen additionally provided with an even harder, carbonaceous cover film.All of the layers display a coefficient of friction that rapidly risesto high levels.

It is the technical objective of this invention to introduce(Al_(y)Cr_(1-y))X-coated work pieces such as chipping, metal-cutting andshaping tools and components used in machine and die construction, aswell as a process for depositing such coatings on a work piece underavoidance of the drawbacks of prior-art methodology.

Examples include work pieces whose coating, at least in terms of theAl/Cr ratio, is of an adjustably uniform or selectably variablecomposition and which at least in certain applications offer greaterwear resistance than has been obtainable with prior-art coatings.

To investigate the wear resistance of (Al_(y)Cr_(1-y))N- or CN-coatedtools, Cr films with different aluminum concentrations were deposited ona variety of work pieces, using an industrial RCS-type Balzers coatingsystem as referred to for instance in EP 1186681, FIG. 3-6, descriptionpage 12, line 26, to page 14, line 9. By reference, said publicationthus becomes an integral part of this patent application. For thatpurpose, the pre-cleaned work pieces were mounted, according to theirdiameter, either on double-rotating or, for diameters under 50 mm, ontriple-rotating substrate carriers while two titanium and fourpowder-metallurgically produced targets of different AlCr alloys wereinstalled in six cathode arc sources on the walls of the coating system.Next, radiant heaters likewise installed in the coating system heatedthe work pieces to a temperature of about 500° C. and, with a biasvoltage of −100 to −200 V applied in an Argon atmosphere at a pressureof 0.2 Pa, the workpiece surfaces were subjected to etch-polishing withAr ions.

Thereupon, by operating the two Ti sources at a power output of 3.5 kW(140 A) in a pure nitrogen atmosphere, a pressure of 3 Pa and asubstrate voltage of −50V over a period of 5 minutes, a TiN bondinglayer about 0.2 μm thick was deposited, followed by the activation ofthe four AlCr sources with a power of 3 kW for a period of 120 minutes,which deposited a film of AlCrN. An optimized transition between thelayers was obtained by simultaneously operating all sources for 2minutes. Thereafter, a nitride layer on an AlCr base was deposited in apure nitrogen atmosphere, again at a pressure of 3 Pa and a substratevoltage of −50V. In principle, the process pressure for each of thesesteps may be set in the range from 0.5 to about 8 Pa, preferably between2.5 and 5 Pa, and for nitride films either a pure nitrogen atmosphere ora mixture of nitrogen and an inert gas such as argon may be used, forcarbonitride films a mixture of nitrogen and a carbonic gas, with theadmixture of an inert gas if necessary. Correspondingly it is possible,when depositing oxygenous or boronic coatings, to admix oxygen or aboronic gas in conventional fashion.

Table 1 shows such characteristics of the layers as theircrystallographic structure, their thickness, their hardness, their wearresistance and the bonding strength of AlCrN films as a function oftheir chemical composition and crystal structure as well as thecomposition of the targets employed.

Process parameters such as target yield, substrate bias voltage, processpressure and temperature are summarized in Table 2.

Table 3 reflects a test sequence in which AlCrN films were depositedusing targets with an Al/Cr ratio equal to 3 and by applying differentsubstrate voltages. The wear resistance was determined using a precisionabrasion tester of the Fraunhofer Institute IST at Braunschweig andemploying for the mensuration of the abrasion rate a modified DIN EN1071-2-based spherical calotte grinding process. Details of that processare contained in Michler, Surf. & Coat. Tech., Vol. 163-164 (2003), page547, column 1 and FIG. 1. By reference, said publication becomes anintegral part of this patent application.

The following will explain this invention in more detail based on anexample and with reference to the attached graphs in which—

FIG. 1 shows XRD spectra of an AlCrN structure with B1 and B4

FIG. 2 shows XRD spectra of AlCrN films as a function of the chemicalAl/Cr composition: A=75/25, C=50/50, D=25/75

As indicated in Table 1 and FIG. 1 and stated by Kawate in“Microhardness and lattice parameter of Cr_(1-x)Al_(x)N films”, J. VacSci. Technol. A 20(2), March/April 2002; p. 569-571, Al concentrationsof greater than 70 At % of the metal content in the film reveal ahexagonal (B4) layer structure while lower Al concentrations display acubic (B1) layer structure. The HV values measured for hexagonal filmswere about 2100 HV_(0.03), while the HV values measured for cubic filmstructures were higher at about 2800-3100 HV_(0.03) (see Table 1). Withhigher Cr concentrations (sample D) the hardness measured was about 2300HV_(0.03). In contrast to the AlN lattice of the high-aluminum coatingsillustrated in FIG. 2 A, this composition displays a CrN lattice asshown in FIG. 2 D.

Subsequent determinations were aimed at the life of AlCrN-coated 6 mmHSS drill bits used on DIN 1.2080 steel with a hardness of 230 HB at afeed rate of 0.12 mm and a cutting speed of 35 m/min as described inExample 1, below. In the process it was found that, contrary to what JP09-041127 describes as a particularly suitable AlyCr1-yN range of1<y≦0.7, a chrome content greater than 0.3 is more advantageous. Whenthe chrome concentration is greater than or equal to 0.8, theperformance in this area of application deteriorates again due to theexisting CrN lattice. Compared to hexagonal AlCrN films in this test,the life extension of those with a cubic structure was 235%.

For layers in a transitional region with an Al content of between 60%and 75 At % it is possible by way of the process parameters to selectnot only the privileged orientation but also the basic structure of thecrystal lattice. As shown in the example of Test B (Table 2), a lowpressure of 1 Pa and a substrate voltage of −50V produced a hexagonalstructure, whereas a pressure range of 3 Pa and a substrate voltage of−50V results in a cubic structure. The hexagonal structure is thusdeposited at a relatively low bias voltage and low pressure while thepreferred cubic structure is deposited at a higher pressure and arelatively higher bias voltage. At higher Al concentrations it is nolonger possible to produce a cubic layer structure.

Work pieces according to this invention therefore feature a cubic(Al_(y)Cr_(1-y))X coating of the following composition: X=N or CN butpreferably N, and 0.2≦y<0.7, preferably 0.40≦Y≦0.68. The structure ofthe film in this case is microcrystalline with an average grain size ofabout 20-120 nm.

Processes according to the invention are characterized by a procedure inwhich a cubic (Al_(y)Cr_(1-y))X layer is deposited with a composition asdefined above. For the cathodic arc process described, targetcompositions with a 75 to 15% aluminum content lend themselvesparticularly well. In the case of a high aluminum content the processparameters must be selected as described in order to produce a cubiccrystal structure.

In that context it will be advantageous to use powder-metallurgicallyproduced and especially cold-pressed targets that may be more solid thanfused or sintered AlCr targets which especially in the case of a high Alcontent tend to contain brittle phases.

Targets of that type are cold-pressed from mixed pulverulent basematerials followed by repeated reshaping for instance in a forgingpress, compacted at temperatures below 660° C. under fluxing andcold-fusion, and brought to a final condition with a theoretical densityof about 96-100%.

It has also been found that in the case of an AlCrN coating that wasdeposited for instance with targets of the Al/Cr=3 composition, thesubstrate bias voltage can affect the wear resistance. As the substratebias voltage is increased, the abrasion resistance decreases (see Table3). Already with a very small negative substrate voltage, notspecifically shown in the Table, of just a few volts (3-10V and anyvoltage in between) it is possible to obtain a significant improvementin comparison with floating substrates (having no external voltagesupply). The wear resistance of Al/Cr=3 reaches its maximum at about−20V, then drops off again at higher voltages. The tests conducted fordetermining the wear pattern suggest an optimal substrate voltage rangeof between 3 and 150V and especially between 5 and 40V, in which range avery low abrasion rate of between 0.4 and 1.0 and especially between 0.4and 0.8 m³m⁻¹N⁻¹ 10⁻¹⁵ has been measured. Similar conditions apply tocubic layers, per this invention, of different Al/Cr compositions, whichdid not reveal any abrasion rates of greater than 1.5 m³m⁻¹N⁻¹ 10⁻¹⁵. Itshould be mentioned, however, that the wear resistance even of coatingsdeposited on floating substrates with a high substrate voltage issubstantially greater than that of conventional TiAlN coatings whoseabrasion coefficient is significantly higher. For example, for a TiAlNfilm deposited in analogous fashion as the AlCrN coatings (Experiment 2,Al 47 At %, Ti 53 At %) an abrasion rate of 3.47 m³m⁻¹N⁻¹ 10⁻¹⁵ wasmeasured.

The process described above, and especially the use ofpowder-metallurgically produced TiAl targets, has made it possible todeposit low-roughness coatings. The HRMS values measured are in therange between 0.1 and 0.2 μm and are thus in the same range as those ofCrN coatings produced in comparable fashion. Further smoothing of thecoatings has been accomplished using a magnetic field generatorencompassing two counter-polarized magnet systems, which generator is sodesigned that the component B₁ of the resulting field, extending in adirection perpendicular to the surface, displays essentially constantsmall or zero values over a major part of that surface. The values ofthe perpendicular magnetic field component B₁ were set at below 30,preferably below 20 and most desirably below 10 Gauss. The HRMS valuesof the (Al_(y)Cr_(1-y))X layers thus deposited were in the 0.05 and 0.15μm range. The magnetic field was generated by two mutuallycounter-polarized coils coaxially positioned behind the target.

It is also possible when depositing (Al_(y)Cr_(1-y))X coatings to useother, preferably highly conductive, nitride or metallic bonding layersor indeed, for certain applications, to dispense with these. Forexample, for achieving a particularly high productivity level it ispossible to apply an AlCr/AlCrN in lieu of a TiN bonding layer, whichallows all arc sources of a coating system to be equipped with AlCrtargets and to increase the coating throughput rate.

It is further possible to deposit gradient coatings for instance with anAl content that is incremented toward the surface, either by using twotypes of targets with different Al/Cr ratios or, starting with a Crand/or CrN bonding layer, bringing about a progressive change in thelayer composition for instance by a continuous or stepwise adjustment ofthe corresponding target output in a coating chamber equipped with bothCr and AlCr targets. The important factor for an industrial applicationof this type of coatings is the ability to reproducibly adjust theprocess parameters essentially over the entire progression of thecoating process and thus over the entire thickness of the film. Minorcompositional fluctuations occurring for instance on a single- ormultiple-rotation substrate carrier can be additionally utilized forproducing a nanostructure over part or all of the thickness of thelayer, i.e. for lamination in the nano or micrometer range. Due to theprocess involved in that case, the use of unalloyed chrome and aluminumtargets will result in the deposition of a more coarsely structured hardfilm than would be the case with alloyed AlCr targets.

Not very suitable for this purpose, however, are prior-art processes inwhich for instance the evaporation of at least one component is eitherdiscontinuous or difficult to control, since that does not allow for areproducible quality of the coating.

It is also possible, of course, to produce this type of coatings inother vacuum coating systems for instance by sputtering, although it maybe necessary to compensate for the low ionization of the process gasinherent in sputtering processes by traditional provisions such asspecial bonding layers, additional ionization etc. in order to obtaincomparable bonding of the film.

Cr_(1-x)Al_(x)N films of this type, having a cubic structure,essentially lend themselves well for coating the most diverse workpieces. Examples include cutting tools such as routers, hobs, spherical,planar and profiling cutters, as well as drills, taps, clearing tools,reamers and indexable inserts for lathes and milling machines or shapingtools such as dies, swages, drawing dies, ejector cores or threadformers. Other examples of advantageous utilization of these protectivelayers include injection molds for instance for injection-molded metalalloys, synthetic resins or thermoplastics, and especially injectionmolds as used in the production of plastic components or of data-storagemedia such as CDs, DVDs and the like. Another application area includesstructural components that must meet stringent requirements in terms ofwear and perhaps also high oxidation resistance. Examples in the pumpand engine industry include sealing washers, pistons, plungers, gears,valve drives, cup rams and rockers, or injection-nozzle valves,compressor shafts, pump spindles, and many denticulated or mortisedcomponents.

Given the essentially similar characteristics of (Al_(y)Cr_(1-y))Xcoatings, they are likely to improve wear resistance when for subsequentlayer systems the target composition and coating parameters are selectedin such fashion that a cubic layer structure is obtained.

(Al_(y)Cr_(1-y))X films are layers in which X=N, C, B, CN, BN, CBN, NO,CO, BO, CNO, BNO, CBNO, but preferably N or CN and 0.2≦y<0.7 andpreferably 0.40≦Y≦0.68.

Accordingly, (Al₆₆Cr₃₃)NO layers with different N/O ratios weredeposited and their properties tested. The coating parameters selectedwere similar to those described above. The settings were 1 to 5 Pa forthe overall pressure, between 20 and 60 sccm for the oxygen flow (theremainder being nitrogen), between −40 to −150V for the substratevoltage, 450° C. for the temperature and a 140 A3.5 kW current for thesource power. The layers produced had O/N ratios of about 0.2, 0.6 and2.2. Various milling tests showed the coatings with a lower oxygencontent to be of superior quality. The results were significantly betterthan those obtained in lifetime tests with conventional TiN or TiCN.

The fact that these (Al_(y)Cr_(1-y))X films offer better glidingqualities than conventional TiAlN coatings opens up interestingpossibilities from both the economic and the ecologic perspectives inconnection with the operation of tools, especially cutting and shapingtools by being able to eliminate or to minimize the amount of lubricantsneeded. With regard to the economic aspects it should be remembered thatthe cost of cooling lubricants especially in the case of cutting toolscan be significantly higher than the cost of the tool itself.

The gliding quality of a coating containing an (Al_(y)Cr_(1-y))X layerper this invention can be further improved by additionally applying anouter slip layer. This slip layer should preferably have a lowerhardness value than the (Al_(y)Cr_(1-y))X film and should have goodlead-in properties.

The slip layer system may be constituted of at least one metal or of thecarbide of at least one metal and dispersed carbon, MeC/C, with themetal being one of group IVb, Vb and/or VIb or silicon. A particularlysuitable example with excellent lead-in properties is a WC/C cover layerwith a hardness that can be selected between 1000 and 1500 HV. CrC/Clayers offer similar characteristics, albeit with a somewhat higherfriction coefficient.

Deep-hole drills thus coated, after producing one to three boreholes,displayed an excellent smoothing of the lead-in cutting surfaces,something that has so far been attainable only with a time-consumingmechanical finishing effort. These properties are also of particularinterest for application on slide-, friction- or roller-exposedcomponents especially when operated with minimal or no lubrication, orwhen at the same time an uncoated opposite companion element is to beprotected.

Other possibilities for creating outer layers with a slip surfaceinclude nonmetallic, diamond-like carbon films or MoS_(x), WS_(x) ortitanium-containing MoS_(x) or MoW_(x) coatings.

In the manner described, the slip layer can be applied directly on the(Al_(y)Cr_(1-y))X film, or on an additional intermediate bonding layerthat may be constituted of a metal, a nitride, a carbide, a carbonitrideor indeed of a gradient layer for instance with a progressive transitionbetween the (Al_(y)Cr_(1-y))X film and the slip layer for assuring abest possible bond of the composite layer system.

For example, it is possible to produce WC/C or CrC/C layers, after theapplication of a sputtered or arc-deposited Cr or Ti bonding layer,preferably by sputtering WC targets with the addition of a carbonaceousgas. The proportion of carbonic gas is increased over time so as toobtain a larger free-carbon percentage in the layer.

Illustrated below are examples of other advantageous applications ofdifferent (Al_(y)Cr_(1-y))X hard-coated tools used in a variety ofcutting operations.

EXAMPLE #1 Milling of Structural Steel

The tool: Hard-metal end-milling cutter

Diameter D=8 mm, number of teeth z=3 Material: Structural steel Ck45,DIN 1.1191

Milling parameters:

Cutting speed v_(f)=200/400 m/min Feed rate v_(?)=2388/4776 mm/minRadial width of contact a_(e)=0.5 mm Axial width of contact a_(p)=10 mmCooling: 5% emulsion Process: Climb milling

Abrasion criterion: Flank wear VB=0.12 mm

Metal content (At %) Life span t at VB = 0.12 mm Experiment Layer Inminutes No. Ti Al Cr v_(c) = 200 m/min v_(c) = 400 m/min 1 (TiCN) 100 —— 71 9 2 (TiAlN)  53 47 — 42 15 3 (AlCrN) B1 — 69.5 30.5 167 40 4(AlCrN) B4 72 28 41 7 5 (AlCrN) B1 — 41.5 58.5 150 12 6 (AlCrN) B1 — 1981 17 4

Example #1 shows a comparison of the life span of coated HM millingtools tested with different cutting parameters.

It is clearly evident that, compared to conventional industriallyemployed coatings such as TiCN and TiAlN, the AlCrN described offerlonger life spans. The results also show that, as in Example #1, thetool life is extended with an augmented Al content, provided the cubicB1 structure is maintained (compare Experiment No. 3, 5, 6). This isattributable primarily to improved oxidation resistance and hardness asthe Al content is augmented (see Table 1). It is especially in dry andhigh-speed processing (e.g. v_(c)=400 m/min) that this excellentoxidation resistance of the AlCrN coating proves advantageous. Apartfrom that, it is noted in this test as well that a shearing of thecrystal lattice from the B1 to the B4 structure causes the wearresistance to deteriorate (compare Experiments 3 and 4).

EXAMPLE #2 Milling Austenitic Steel

The tool: Hard-metal end-milling cutter

Diameter D=8 mm, number of teeth z=3 Material: Austenitic steel X 6CrNiMoTi 17 12 2, DIN 1.4571

Milling parameters:

Cutting speed v_(c)=240 m/min Tooth feed rate f_(z)=0.08 mm Radial widthof contact a_(e)=0.5 mm Axial width of contact a_(p)=10 mm Cooling: 5%emulsion Process: Climb milling

Abrasion criterion: Flank wear VB=0.1 mm

Metal Tool life content (At %) travel I_(?) at Experiment Layer VB = 0.1mm in No. Ti Al Cr meters 7 (TiCN) 100 — — 33 8 (AlTiN)  35 65   — 45 9(AlCrN) B1 — 69.5 30.5 54

Example #2 shows a comparison of the life span of coated HM millingtools. Here as well, the AlCrN layer resulted in improved wearresistance compared to the hard films currently used in the industry.The extended life span through the use of AlCrN was obtained due, forone, to an as yet undocumented lower propensity for streaking—comparedto Ti in TiAlN layers—of Cr as the second element of the alloy, and, foranother, to the good wear resistance, shown in Table 1, of the AlCrNfilms (A, B, D) of this invention, while at the same time offering highhardness values.

EXAMPLE #3 Milling Hardened Steel

The tool: Hard-metal ball-head milling tool

Diameter D=10 mm, number of teeth z=2 Material: K340 (62HRC),corresponds to C 1.1%, Si 0.9%, Mn 0.4%, Cr 8.3%, Mo 2.1%, V 0.5%

Milling parameters:

Cutting speed v_(c)=0-120 m/min Tooth feed rate f_(z)=0.1 mm Radialwidth of contact a_(e)=0.2 mm Axial width of contact a_(p)=0.2 mmCooling: Dry Process: Climb and upcut milling, finishing

Abrasion criterion: Flank wear VB=0.3 mm

Metal content Tool life travel I_(f) at Experiment (At %) Layer VB = 0.3mm in No. Ti Al Cr meters 10 (TiAlN) 53 47 — 70 11 (AlCrN) B1 — 69.530.5 90 12 (AlTiN) 35 657 — 90 13 (AlCrN) B1 — 69.5 30.5 130

Examples #3 and #4 show an improved tool life travel of the AlCrN filmsas compared to TiAlN coatings currently used in the industry. AlCrN thusalso lends itself particularly well to dry machining that involvesdemanding requirements in terms of oxidation and wear resistance.

EXAMPLE #4 Rough-Milling of Tool Steel

The tool: Hard-metal end-milling cutter

Diameter D=10 mm, number of teeth z=4 Material: Tool steel X 38 CrMoV 51, DIN 1.2343 (50HRC)

Milling parameters:

Cutting speed v_(c)=60 m/min Tooth feed rate f_(z)=0.02 mm Radial widthof contact a_(e)=2 mm Axial width of contact a_(p)=10 mm Cooling: DryProcess: Climb milling, roughing

Abrasion criterion: Flank wear VB=0.1 mm

EXAMPLE #5 Drilling Tool Steel

The tool: HSS drill (S 6-5-2). Diameter D=6 mm

Material: Tool steel X 210 Cr 12, DIN 1.2080 (230HB)

Drilling parameters:

Cutting speed v_(c)=35 m/min Feed rate f=0.12 mm Depth of bore z=15 mm,pocket hole Cooling: 5% emulsion

Abrasion criterion: Torque cutoff (corresponds to a corner abrasion of≧0.3 mm)

Metal content Tool life travel Experiment (At %) Layer [number ofholes/μm No. Al Cr layer thickness] 14 (AlCrN) B1 19 81 21 15 (AlCrN) B141.5 58.5 52 16 (AlCrCN) B1 41.5 58.5 65 17 (AlCrN) B1 69.5 30.5 108 18(AlCrN) B4 72 28 46

Example #6 shows a comparison of HSS drills with AlyCr1-yN/AlyCr1-yCNlayers having different Al concentrations, with the number of holesstandardized over the layer thickness.

The layers were produced along the parameters per Table 2. As can beseen, the life span is extended as the aluminum content is increased, upto an aluminum concentration of just under 70% of the overall metalcontent. Any further increase, however, leads to the deposition of alayer with a hexagonal crystal structure and thus to a distinct drop inperformance. A performance significantly better than that attainable byprior-art methods (Experiment #18) manifested itself in the rangebetween 41.5% and 69.5% (Experiments #15, 17).

EXAMPLE #6 Deep-Hole Drilling 5xD in Ck45

The tool: Hard-metal drill. Diameter D=6.8 mm

Material: Structural steel 1.1191 (Ck45)

Drilling parameters:

Cutting speed v_(c)=120 m/min Feed rate f=0.2 mm Depth of bore z=34 mm,pocket hole Cooling: 5% emulsion

Abrasion criterion: Corner abrasion VB=0.3 mm)

Metal content Tool life span t at Experiment (At %) Layer VB = 0.3 mm inNo. Ti Al Cr Number of boreholes 18 (TiAlN) 70 30 — 890 19 (TiAlN) 53 47— 1135 20 (AlCrN) B1 — 69.5 30.5 2128

Example #6 shows an improved tool life travel with the AlCrN layer ascompared to TiAlN films currently used for drilling purposes in theindustry. In this case the enhanced abrasive wear resistance of theAlCrN coating per this invention has proved valuable.

In addition, drill bits when coated as in Experiment #20 and after theapplication of a Cr bonding layer, were provided with a WC/carbon sliplayer, which, with all other test conditions being identical, resultedin a significantly extended tool life. Simultaneously performed torquemeasurements revealed a substantially lower torque than encounteredwithout a slip layer. Moreover, the bores displayed an improved surfacequality and, until just before the end of the tool life, nodiscoloration due to an excessive thermal load was detectable.

EXAMPLE #7 Tapping 2xD in Austenitic Steel

The tool: HSS tap for thread size M8

Material: Austenitic steel 1.4571 (X6CrNiMoT117/12/2)

Cutting parameters:

Cutting speed v_(c)=3 m/min

Depth of thread: 2XDType of thread: Pocket holeNumber of threads: 64

Cooling: 5% emulsion

Abrasion criterion: Torque pattern over the number of threads, visualinspection of wear after 64 threads.

Metal content (At %) Max. Dia. Experiment Layer Cutting torque Visualwear No. Ti Al Cr [Nm] (1) 21 (TiCN) 100 — — 4.72 + 22 (AlCrN) B1 — 69.530.5 4.05 ++ 23 (AlCrN) B1 — 41.5 58.5 4.23 +++ 24 (AlCrN) B1 — 19 814.27 + Explanation of (1) + satisfactory wear pattern in screw tapping++ good wear pattern in screw tapping +++ very good wear pattern inscrew tapping

Compared to prior art (TiCN), all AlCrN films make it possible to reducethe mean maximum cutting torque. Moreover, the very good wear resistanceof the layers with a higher aluminum content results in an improved wearpattern compared to TiCN. On the other hand, this example shows that,presumably due to the adhesive tendency of aluminum that leads tomaterial streaking and ultimately to peeling, the coating per Experiment#23 offers a better wear pattern than that of #22.

In addition, taps when coated as in Experiments #22 and #23 and afterthe application of an AlCr bonding layer, were provided with a WC/carbonslip layer, or, after the application of a Ti bonding layer, with aTi-containing MoS₂ layer, which again, with all other test conditionsbeing equal, resulted in an extended tool life and a qualitativelybetter surface finish of the work piece.

EXAMPLE #8 Hob-Milling of Cr—Mo Steel

The tool: Hob cutter

Material: DIN S6-7-7-10 (ASP60) Diameter D=80 mm, length L=240 mm,module m=1.5

25 chip grooves

Angle of pressure α=20°

Basic rack tooth profile: 2, number of teeth: 50, pitch: 25 mm

Material: Cr—Mo steel DIN 34CrMo4

Cutting parameters:

Cutting speed v_(c)=260 m/min Feed rate=2 mm/rev Quantity: 300 Cooling:Dry cut, compressed air for chip removal

Metal content (At %) Experiment Layer Wear of cutting edge in [mm] No.Ti Al Cr Flank wear Crater wear 25 (TiCN) 100 — — 0.32 0.062 26 (TiAlN) 53 47 — 0.25 0.042 27 (AlCrN) B4 72 28 0.29 0.053 28 (AlCrN) B1 — 19 810.26 0.051 29 (AlCrN) B1 — 41.5 58.5 0.13 0.022 30 (AlCrN) B1 — 69.530.5 0.14 0.018

The Experiments 25 to 30 involved the dry-cut testing of different hobcutters of powder-metallurgically produced high-speed steel (HSS)provided with different coatings. The tools coated with films accordingto this invention (Experiments 29 and 30) offer significantly improvedperformance compared to hobbers coated with traditional TiCN or TiAlNfilms. It can also be seen that AlCrN layers with a low (#28) or, in thepresence of a hexagonal crystal structure (#27), excessively high Alcontent provide diminished wear protection.

The following Examples No. 31 through 33 again show the clearly superiorcharacteristics of an AlCrN layer according to this invention, with acubic crystal lattice, an essentially stoichiometric nitrogen percentageand an Al content of 66%. In this case, hob cutters produced from PM HSSand, respectively, hard metal were tested both under dry-cutting andemulsion-lubricated cutting conditions.

Experiment #31: Hob Cutting

The tool: PM HSS

Diameter D=80 mm, length L=240 mm Material: 16 Mn Cr S

Cutting speed: 180 m/min., dry

(Al_(0.42)Ti_(0.58))N, Balinite NANO: Quantity 1,809(Al_(0.63)Ti_(0.37))N, Balinite X.CEED: Quantity 2,985(Al_(0.00)Cr_(0.34))N: Quantity 5,370 Experiment #32: Hob Cutting

The tool: Hard metal (HM)

Diameter D=60 mm, length L=245 mm Module: 1.5 Pressure angle_(—)=20°Material: 42 CrMo4

Cutting speed: 350 m/min, dry

(Al_(0.41)Ti_(0.59))N, Balinite X.TREME: Quantity 1,722(Al_(0.63)Ti_(0.37))N, Balinite X.CEED: Quantity 2,791(Al_(0.66)Cr_(0.34))N: Quantity >3,400 Experiment #33: Hob Cutting

The tool: PM HSS

Module 2.5 Material: 16MnCrS

Cutting speed: 140 m/min, emulsion

TiCN, BALINITE B: Quantity 1,406 (Al_(0.43)Ti_(0.58))N, Balinite NANO:Quantity 1,331 (Al_(0.66)Cr_(0.34))N: Quantity 1,969

Additional tests, not described here in any detail, yielded goodstability even in higher cutting speed ranges as high as v_(c)=450m/min. Similarly, the life span of coated hard-metal hob cutters wasextended quite significantly in wet-cutting but especially also in dryprocessing operations.

EXAMPLE #9 Rough Milling of Tool Steel

The tool: HSS end milling cutter

Diameter D=10 mm, number of teeth z=4 Material: Tool steel X 40 CrMoV 51, DIN 1.2344 (36HRC)

Milling parameters:

Cutting speed v_(c)=60 m/min Tooth feed f_(z)=0.05 mm Radial width ofcontact a_(e)=3 mm Axial width of contact a_(p)=5 mm Cooling: 5%emulsion Process: Climb milling, roughing

Abrasion criterion: Flank wear VB=0.1 mm

Metal content Tool life travel I_(f) at Experiment (At %) Layer VB = 0.1mm in No. Ti Al Cr meters 34 (AlTi) N 35 65 — 6-8 35 (AlTi) N 58 42 —3-4 36 (AlTi) CN 50 50 — 3-4 37 TiCN 100  — —  8-11 38 (AlCr) N BL 66 3612-21 39 (AlCr) N Pulsed 66 36 21-28 40 (AlCr) N — 66 36 12-18 BL =bonding layer of TiN Pulsed = pulsed bias

EXAMPLE #10 Longitudinal Turning of Outer Diameter on Case HardenedSteel

The tool: Lathe cutter with brazed-in CBN insert

Material: Case-hardened steel 16 MnCr 5, DIN 1.7131(49-62 HRC)

Lathe-turning parameters: Carbide- and mild-steel machining withmulti-step cutting and partly reduced wall thickness

Cooling: Dry

Abrasion criterion: Quantities up to where a flank wear of VB=0.1 mm isreached.

Metal content Experiment (At %) Layer Tool life quantity No. Ti Al Cr atVB = 0.1 mm 41 (AlTi) N 35 65 — 90 42 (AlCr) N 66 36 144

Similar results were achieved with powder-metallurgically producedcermets consisting of a TiN, TiC or Ti(CN) hard phase to which in a fewindividual cases molybdenum and/or tantalum was added. The binder phaseused in that process was Ni or Ni/Co.

EXAMPLE #11 Forming Threads in Galvanized Plate Metal Experiment #43:

The tool: HSS M9 thread former

Material: DC01, corresponding to DIN 1.0330, St 12 ZE

Core hole diameter: 8.34 mmCutting parameters: 55 m/sRotary cutting speed: 2000 RPMReverse cutting speed: 3600 RPM

Lubrication: S26 CA TiN: 3200 threads TiCN: 3200 threads TiAlN: 3500threads (Al_(0.66)Cr_(0.34))N: 8800 threads

Tests with coated CBN (cubic boronitride) and cermet tools: Indexableinserts consisting of different CBN sintered materials with a CBNcontent of between 30 and 99 percent by volume, the remainder beingbinders, were coated, on the one hand, with conventional TiAlN layers asper Experiment #8, and on the other hand with AlCrN layers according tothis invention and as shown in Experiments 3, 5 and 6. For the etchingand coating process, however, because of the nonconductive nature of theCBN sintered material, a pulsed substrate bias was applied in the mediumfrequency range and by preference in a frequency range from 20 to 250kHz.

For materials with a CBN content of up to 90% a pulverulent binder wasused that consisted of at least one of the elements of the followinggroup: The nitride, carbide, boride and oxide of the Ti, V or Cr group,i.e. IVa, Va and VIa elements as well as aluminum or Al alloys.

For materials with a CBN content of up to 95% a pulverulent binder wasused that consisted of titanium nitride and at least one of the elementsof the following group: Cobalt, nickel, tungsten carbide, aluminum or analuminum alloy.

For materials with a CBN content higher than 90%, use was also made of apulverulent binder consisting of titanium nitride and at least one ofthe elements of the following group: Boride or boronitride of thealkaline or alkaline-earth metals.

Most of the subsequent turning and milling tests revealed asignificantly better wear resistance than that of TiAlN coatings. Thesame was found in a particularly laborious longitudinal outer-diameterturning test that involved the machining, in part by discontinuousstepwise cutting, of an only partially hardened shaft with a complexgeometric configuration.

1. Work piece coated with a system of film layers comprising at leastone film composed of (Al_(y)Cr_(1-y))X, where X=N, C, B, CN, BN, CBN,NO, CO, BO, CNO, BNO or CBNO and 0.415≦y≦0.695, with the compositionwithin said (Al_(y)Cr_(1-y))X film being either essentially constant orvarying over the thickness of the (Al_(y)Cr_(1-y))X film continually orin steps, said (Al_(y)Cr_(1-y))X film having a cubic crystal structureand a rate of wear less than or equal to 1.5×10⁻¹⁵ m³m⁻¹N⁻¹, said workpiece constituting one of the following tools: a milling tool, a hob,(spherical-head) ball nose mill, planar or profiling cutter, a clearingtool, reamer, (indexable tip) insert for turning and milling, a die oran injection mold.
 2. Work piece coated with a system of film layerscomprising at least one film composed of (Al_(y)Cr_(1-y))X, where X=N,C, B, CN, BN, CBN, NO, CO, BO, CNO, BNO or CBNO and 0.415≦y≦0.695, withthe composition within said (Al_(y)Cr_(1-y))X film being eitheressentially constant or varying over the thickness of the(Al_(y)Cr_(1-y))X film continually or in steps, said (Al_(y)Cr_(1-y))Xfilm having a cubic crystal structure and a rate of wear less than orequal to 1.5×10⁻¹⁵ m³m⁻¹N⁻¹, said work piece constituting a machinecomponent.
 3. Work piece as in claim 2, wherein said component is asealing washer, a gear, a piston, a part of a valve drive or a needlefor an injection nozzle, or that it is toothed.
 4. Work piece as inclaim 1, wherein the tool is a forming tool of an upper die, a bottomswage, a drawing die, an ejector core or a thread former.
 5. Work pieceas in claim 1, wherein the tool is an injection-molding tool forproducing a molded plastic part or a data storage medium.
 6. Work pieceas in claim 1, wherein the tool features a CBN or Cermet base unit orthat the tool is a CBN or Cermet (indexable tip) insert.
 7. Work pieceas in claim 1, wherein a Vickers pyramid hardness of the(Al_(y)Cr_(1-y))X film is 2300 to
 3100. 8. Work piece as in claim 1,wherein a layer structure of the (Al_(y)Cr_(1-y))X film ismicrocrystalline with an average grain size of 20 to 120 nm.
 9. Workpiece as in claim 1, wherein a bonding layer is applied between the workpiece and the (Al_(y)Cr_(1-y))X film.
 10. Work piece as in claim 9,wherein said bonding layer encompasses at least one of the metals ofgroup IV, V or subgroup VI, or aluminum.
 11. Work piece as in claim 9,wherein said bonding layer includes at least one nitride, carbide orcarbonitride of one or several metals of subgroup IV, V or VI.
 12. Workpiece as in claim 9, wherein at least one (Al_(y)Cr_(1-y))X film isadditionally coated with a slip layer.
 13. Work piece as in claim 12,wherein said slip layer encompasses a carbide of at least one metal withdispersed carbon, MeC/C wherein Me is selected from among group IVb, Vband VIb metals and silicon, a diamond-like carbon layer, a Si- ormetallic diamond-like carbon layer, a MoS_(x), a WS_(x) or atitanium-containing MoS_(x) or MoW_(x) layer.
 14. PVD process fordepositing at least one (Al_(y)Cr_(1-y))X film on a work piece, whereX=N, C, B, CN, BN, CBN, NO, CO, BO, CNO, BNO, CBNO and 0.415≦y≦0.695,comprising the steps of installing at least one work piece in a vacuumcoating system with at least one Al_(z)Cr_(1-z) target, where0.25≦z<0.75, operating said system at a pressure of 0.5 to 8 Pa with theaddition of a nitrogen-, carbon-boron- or oxygen-containing reactive gasand applying on the work piece of a substrate voltage of between −3 and−150V, as an arc or sputtering source, wherein the constituentcomposition within the said at least one (Al_(y)Cr_(1-y))X film iseither essentially constant or varies either continuously or in stepsover the thickness of the film, said at least one (Al_(y)Cr_(1-y))X filmhaving a cubic crystal structure and a rate of wear less than or equalto 1.5×10⁻¹⁵ m³m⁻¹N⁻¹, said work piece being selected from among thefollowing tools: a milling tool, a hob, (spherical-head) ball nose mill,planar or profiling cutter, a clearing tool, reamer, (indexable tip)insert for turning and milling, a die, an injection mold or a machinecomponent.
 15. PVD process as in claim 14, wherein X=N and the reactivegas is nitrogen or oxygen.
 16. PVD process as in claim 14, wherein thesubstrate voltage is pulsed.
 17. PVD process as in claim 14, wherein theAl_(z)Cr_(1-z) target is a powder-metallurgically produced target. 18.PVD process as in claim 17, wherein the target is produced bycold-pressing starting material in powder form with repeated subsequentreshaping, at temperatures under 660° C., densification by fluxing andcold fusion, and transformation into its final state with a theoreticaldensity at about 96 to 100%.
 19. Process comprising the steps ofmachining a material with a tool recited in claim 1, wherein saidmachining using said tool is performed without the addition oflubricants or cooling agents.
 20. Process as in claim 19, wherein thetool is a hard-metal or HSS hob (cutter) and the cutting speed is 60 to450 m/min.
 21. Process as in claim 19, wherein the tool is anend-milling, (spherical-head) ball-nose-mill or a roughing cutter.